US2959613A - Oxidation process - Google Patents
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- US2959613A US2959613A US709751A US70975158A US2959613A US 2959613 A US2959613 A US 2959613A US 709751 A US709751 A US 709751A US 70975158 A US70975158 A US 70975158A US 2959613 A US2959613 A US 2959613A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
Definitions
- This invention relates to a process of liquid phase oxidation.
- a process for the oxidation of organic compounds conducted in the liquid phase by means of molecular oxygen or ozone employing as catalyst at least one metal of variable valence, in which a saturated aliphatic monocarboxylic acid is present as medium, or product of reaction, characterised in that the oxidation is conducted in the presence of cations corresponding to a concentration within the. range.
- the gram mole specified in the above definition is taken as the sum of the gram mole fractions of the said compounds. While it is desirable, it
- any basic ions is within the scope of .the invention it is preferred to use those of the alkali metals or alkaline earth metals: lithium, sodium, potassium, rubidium, caesium, calcium, strontium and barium. Beryllium, magnesium, zinc and cadmium are also effective but to a lesser degree. Suitable compounds of the metals are, for example, the oxides, hydroxides, carbonates, phosphates, halides, or carboxylates, e.g. acetates, propionates, naphthenates. Basic ions seem to modify the catalyst. i
- suitable catalysts comprise, for example, compounds of manganese, cobalt, lead or cerium.
- icatalyst's are the mixed bromides of manganese and cobalt.
- This process is of especial value for the production of saturated aliphatic acids from the corresponding aldehydes, especially those containing in the molecule from 2 to 15 carbon atoms.
- the following procedure is especially suitable for the oxidation of propionaldehyde, but is also applicable to the oxidation of the other aldehydes.
- a solvent e.g. an aliphatic acid.
- the metal of variable valence is preferably either manganese or cobalt or combinations thereof, added in a total metal concentration of between 1.0 and 0.00001 gram atom per gram mole of propionaldehyde, more usually within the range 0.001 to 0.00001 gram atom/ gram mole of aldehyde.
- Basic ions of the types defined above are added at a concentration of from 0.25 to 0.00025 gram.
- Oxidation temperatures may be between 0 and 150 C., and it is an advantage of the process that higher oxidation temperature may be used in the presence of basic ion, as this latter prevents degradative oxidation of the product.
- a higher oxidation temperature enables the reaction to be controlled by water cooling and hence avoids refrigeration, whichis expensive.
- the oxidising gas may be air or oxygen at atmospheric pressure, elevated pressure, or even subatmospheric pressure.
- Means for dispersing the gas in the liquid may be provided or alternatively for dispersing the liquid in the gas. Such processes may be operated batchwise or continuously.
- the oxidation of alkylated compounds of aromatic in the presence of an aliphatic monocarboxylic acid and of a metal of variable valence can be conducted at, for example, 50 to 300 C. and at atmospheric or super-. atmospheric pressures of up to 200 atmospheres.
- the catalysts may be employed as compounds of the metals such as their carboxylates, e.g. the acetates, propionates, nonanoates, naphthenates, of manganese, cobalt, lead cerium, vanadium etc. Improved results are obtained in this process when the catalyst comprises halogen or a halide, especially bromine, in addition Especially suitable It is'often convenient to introduce the basic ion in chemical combination with bromine, e.g. as sodium, potassium, calcium or barium bromide. Suitable proportions of the catalytic substances are from 1 to 0.0005 gram atom of total metal per gram mole of oxidisable starting material,
- the ratio of the one metal to the other may be varied within these ranges of total metal.
- the ratio of manganese to cobalt is about 2:1, although up to about 9:1 gives good results.
- Suitable proportions of manganese dibromide (MnBr AH O) and of cobaltous bromide (CoBr .6H O) are, respectively, 0.1 to 200%, preferably 0.65 to 0.85%, and 0.05 to 100%, preferably I 0.33 to 0.48% by'weight of the compound to be oxidised,
- halogens especially bromine may also be present, e.g. as the halides of metals of variable valence. 1f halogen is present the basic ion may be introduced as a compound of the halogen, e.g. sodium bromide or barium bromide. In this process fairly wide ranges of temperature may be used, e.g. 0 to 150 C. Pressure is not necessary, but may be used if desired. 1- if;
- alkyl aromatic hydrocarbons which can be oxidised to the corresponding acids according to the process are: the xylenes which yield the corresponding phthalic acids; the diisopropyl benzenes which also yield the corresponding phthalic acids; toluene or cumene which .yield benzoic' acid; mesitylene which yields trimesic acid; methylnaphthalenes which yield naphthoic acids; and
- esters such as benzylbenzoate which yields benzoic 'acid
- the yle 5 rep c c1 exit gas stream contained an average of 29.7 volume Examples of hetel-AoFychc compounds of w Ch?- percent of carbon dioxide and at the end of this period 23?; gi ggfi gggg g gijg afi 2 522 pyndmes which carbon dioxide was still being vigorously evolved.
- hydrocarbons of aromatic character subthls 9 gram of q bromlde 5 added and 1 evolution of carbon dioxide and format1on of water stituted by at least one alkyl, haloalkyl or closely related ceased Showin Su mssion of oxidative degradation of oxygenated derivative of an alkyl or haloalkyl group and 15 the pnjpionic agcid the hour followino the f$g 2 6 ffsii i ii gjigfii i gf 2 :33 dition of the sodium bromide .the average carbon dioxide i (Rjalkyl, a W21) NHCOR 3 or content of the exit gas stream was 0.5 volume percent.
- Examples of such compounds are: A charge consisting of 600 grams of propionic acid, paraand meta-chlorotoluene;paraand meta-toluene sul- 0.59 gram of cobalt bromide (CoBr .6H O) and 1.14 phonamides; paraand meta-cresyl benzoates; para- 26 grams of manganese bromide (MnBr .4H O) was heated toluene sulphonic acid; methyl para-toluene suphonate; to 180 C. in a stainless steel reactor under an oxygen para-toluamide; beta-picolincs.
- the halo-methylation pressure of 150 p.s.i.g., and oxygen at a pressure of 150 products of toluene or benzene, especially the chlorop.s.i.g. was introduced at a rate of 200 litres/hour (measand bromoones, may also be oxidised according tothe ured at atmospheric pressure into the bottom of the reinvention to the corresponding carboxylic acids. 30 actor through a /s" bore standpipe for 8 hours. Samples The molecular oxygen may be introduced as air or of the exit gas were analysed periodically for oxides of diluted air or as ozonated air. carbon and the figures obtained were as follows:
- EXAMPLE 5 1 In a blank experiment oxygen in well dispersed form was passed at the rate of 12 litres per hour through 200 grams of propionic acid containing 1.0 gram of COBI'26H2O (ii) Operation according to the invention The above experiment was repeated in identical manner except that 6.0 grams of sodium hydroxide was 6 added. The following results were obtained.
- the off-gas from the reactor was mixed with air fed at 12 litres/ hour and frequent Orsat analyses of the mixtures were carried out for oxygen and carbon oxides. Oxygen uptake was rapid and almost complete, and ceased after 5 hours. Thereafter the oxidation was stopped.
- EXAMPLE 7 It has been shown above that the presence of basic ion greatly decreases the oxidative degradation of propionic acid. The data given below show that the presence of alkali metal ion does not adversely aifect the oxidation of an alkyl aromatic compound in propionic acid as solvent.
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Description
h -cl f? United States Patent- OXIDATIGN PROCESS Gordon Howard Whitfield, Norton-on-Tees, England, assignor to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed Jan. 20, 1958, Ser. No. 709,751
Claims priority, application Great Britain Feb. 8, 1957 8 Claims. (Cl. 260-524) This invention relates to a process of liquid phase oxidation.
Prior to the present invention there was a large number of processes for the oxidation of organic compounds in the liquid phase by means of oxygen or ozone containing gases. Included among these were a process for the oxidation of aliphatic aldehydes to the corresponding carboxylic acids using catalysts of variable valence such as man ganese, cobalt, or lead, acetates; and a process for the oxidation of alkyl aromatic hydrocarbons to the corresponding carboxylic acid using as catalyst a metal or mixture of metals of variable valence, if desired together with halogen or a halide, e.g. bromine, which was some times conducted in the presence of a solvent, e.g. a lower aliphatic monocarboxylic acid.
We have found that in processes of these sorts the aliphatic carboxylic acid is degraded and that the efliciency of the process falls because of lower yield, and/or the operating costs rise because of degradation of the relative:
1y expensive aliphatic acid and of the need for removing the degradation products. We have now found that in 7 these processes the aforesaid disadvantages may 'be considerably decreased by arranging for the presence --in the reaction medium of basic ions.
According to this invention there is provided a process for the oxidation of organic compounds conducted in the liquid phase by means of molecular oxygen or ozone employing as catalyst at least one metal of variable valence, in which a saturated aliphatic monocarboxylic acid is present as medium, or product of reaction, characterised in that the oxidation is conducted in the presence of cations corresponding to a concentration within the. range.
of from 0.25 to 0.00025 gram atom per gram mole of total organic compounds, preferably from 0.05 to 0.0025
gram atom per gram mole aforesaid. If several organic compounds are present, then the gram mole specified in the above definition is taken as the sum of the gram mole fractions of the said compounds. While it is desirable, it
is not necessary, that all of the cation is in ionic'form.
While the use of any basic ions is within the scope of .the invention it is preferred to use those of the alkali metals or alkaline earth metals: lithium, sodium, potassium, rubidium, caesium, calcium, strontium and barium. Beryllium, magnesium, zinc and cadmium are also effective but to a lesser degree. Suitable compounds of the metals are, for example, the oxides, hydroxides, carbonates, phosphates, halides, or carboxylates, e.g. acetates, propionates, naphthenates. Basic ions seem to modify the catalyst. i
In the oxidation of aliphatic aldehydes to acids according to the process, suitable catalysts comprise, for example, compounds of manganese, cobalt, lead or cerium.
- to r the metal of variable valence.
icatalyst's are the mixed bromides of manganese and cobalt.
This process is of especial value for the production of saturated aliphatic acids from the corresponding aldehydes, especially those containing in the molecule from 2 to 15 carbon atoms. The following procedure is especially suitable for the oxidation of propionaldehyde, but is also applicable to the oxidation of the other aldehydes. With higher aldehydes it may be desirable to use a solvent, e.g. an aliphatic acid.
The metal of variable valence is preferably either manganese or cobalt or combinations thereof, added in a total metal concentration of between 1.0 and 0.00001 gram atom per gram mole of propionaldehyde, more usually within the range 0.001 to 0.00001 gram atom/ gram mole of aldehyde. Basic ions of the types defined above are added at a concentration of from 0.25 to 0.00025 gram.
atom per gram mole of organic compound present, usual: ly from 0.05 to 0.0025 gram atom per gram mole, added e.g. as carboxylate such as propionate, acetate; or as mono-, dior tri-basic phosphates; or as halides etc. Oxidation temperatures may be between 0 and 150 C., and it is an advantage of the process that higher oxidation temperature may be used in the presence of basic ion, as this latter prevents degradative oxidation of the product. A higher oxidation temperature enables the reaction to be controlled by water cooling and hence avoids refrigeration, whichis expensive. The oxidising gas may be air or oxygen at atmospheric pressure, elevated pressure, or even subatmospheric pressure. Means for dispersing the gas in the liquid may be provided or alternatively for dispersing the liquid in the gas. Such processes may be operated batchwise or continuously.
The oxidation of alkylated compounds of aromatic in the presence of an aliphatic monocarboxylic acid and of a metal of variable valence can be conducted at, for example, 50 to 300 C. and at atmospheric or super-. atmospheric pressures of up to 200 atmospheres. The catalysts may be employed as compounds of the metals such as their carboxylates, e.g. the acetates, propionates, nonanoates, naphthenates, of manganese, cobalt, lead cerium, vanadium etc. Improved results are obtained in this process when the catalyst comprises halogen or a halide, especially bromine, in addition Especially suitable It is'often convenient to introduce the basic ion in chemical combination with bromine, e.g. as sodium, potassium, calcium or barium bromide. Suitable proportions of the catalytic substances are from 1 to 0.0005 gram atom of total metal per gram mole of oxidisable starting material,
preferably 0.1 to 0.001 gram atom of total metal per gram mole aforesaid; and of halogen, e.g. bromine,'from' 2 to '0.001 gram atoms per gram mole of starting material, preferably from 0.2 to 0.002 gram atom per gram mole aforesaid. The ratio of the one metal to the other may be varied within these ranges of total metal. Preferably the ratio of manganese to cobalt is about 2:1, although up to about 9:1 gives good results. Suitable proportions of manganese dibromide (MnBr AH O) and of cobaltous bromide (CoBr .6H O) are, respectively, 0.1 to 200%, preferably 0.65 to 0.85%, and 0.05 to 100%, preferably I 0.33 to 0.48% by'weight of the compound to be oxidised,
If desired halogens, especially bromine may also be present, e.g. as the halides of metals of variable valence. 1f halogen is present the basic ion may be introduced as a compound of the halogen, e.g. sodium bromide or barium bromide. In this process fairly wide ranges of temperature may be used, e.g. 0 to 150 C. Pressure is not necessary, but may be used if desired. 1- if;
assuming a molecular weight of and proportionally for other compounds.
Examples of alkyl aromatic hydrocarbons which can be oxidised to the corresponding acids according to the process are: the xylenes which yield the corresponding phthalic acids; the diisopropyl benzenes which also yield the corresponding phthalic acids; toluene or cumene which .yield benzoic' acid; mesitylene which yields trimesic acid; methylnaphthalenes which yield naphthoic acids; and
esters such as benzylbenzoate which yields benzoic 'acid,
Patented Nov. 8, 1960 and methyl para-toluate, which yields methyl hydrogen terephthalate. However, it has been found difiicult to oxidise tertiary carbon atoms directly attached to a carbon of the ring. Examples of oxygenated derivatives 4 EXAMPLE 2 This experiment was conducted in the manner of Example 1 with a charge consisting of propionic acid (200 grams), CBr 6I-1 O (1.0 gram), Co(OAc) 4H O (5.0
which can be oxidised to the corresponding acids accord- 5 grams) and MnBr 4H O (0.1 gram). Well dispersed mg to process beniyl i WhlFh f hen oxygen was passed at a rate of 12 litres/hour through the 201C and; benzald-ehyde winch yields benzolc acldiacet? boiling solution and water was continually removed as E- i Ta i g ifi acld; and paratolmc and formed. Throughout a four hour oxidation period the yle 5 rep c c1 exit gas stream contained an average of 29.7 volume Examples of hetel-AoFychc compounds of w Ch?- percent of carbon dioxide and at the end of this period 23?; gi ggfi gggg g gijg afi 2 522 pyndmes which carbon dioxide was still being vigorously evolved. At Moreover, hydrocarbons of aromatic character subthls 9 gram of q bromlde 5 added and 1 evolution of carbon dioxide and format1on of water stituted by at least one alkyl, haloalkyl or closely related ceased Showin Su mssion of oxidative degradation of oxygenated derivative of an alkyl or haloalkyl group and 15 the pnjpionic agcid the hour followino the f$g 2 6 ffsii i ii gjigfii i gf 2 :33 dition of the sodium bromide .the average carbon dioxide i (Rjalkyl, a W21) NHCOR 3 or content of the exit gas stream was 0.5 volume percent. -O'COR (R=alkyl, aryl or H), SO R (R=alkyl, aryl or H), -CONRR" (R=alkyl, aryl or H), NRR" EXAMPLE 3 (R=alkyl, aryl), benzoyl, substituted benzoyl or alkyl Blank carboxylic ester, can also be oxidised to the corresponding carboxylic acids. Examples of such compounds are: A charge consisting of 600 grams of propionic acid, paraand meta-chlorotoluene;paraand meta-toluene sul- 0.59 gram of cobalt bromide (CoBr .6H O) and 1.14 phonamides; paraand meta-cresyl benzoates; para- 26 grams of manganese bromide (MnBr .4H O) was heated toluene sulphonic acid; methyl para-toluene suphonate; to 180 C. in a stainless steel reactor under an oxygen para-toluamide; beta-picolincs. The halo-methylation pressure of 150 p.s.i.g., and oxygen at a pressure of 150 products of toluene or benzene, especially the chlorop.s.i.g. was introduced at a rate of 200 litres/hour (measand bromoones, may also be oxidised according tothe ured at atmospheric pressure into the bottom of the reinvention to the corresponding carboxylic acids. 30 actor through a /s" bore standpipe for 8 hours. Samples The molecular oxygen may be introduced as air or of the exit gas were analysed periodically for oxides of diluted air or as ozonated air. carbon and the figures obtained were as follows:
Time: hours 0.25 1.25 2.25 3.25 4.25 5.25 0.25 7.25
Volumwmentmofl-Wf- {88' 2:3 3:3 1:? ii? 28 i3 :13: i3
EXAMPLE 5 1 In a blank experiment oxygen in well dispersed form was passed at the rate of 12 litres per hour through 200 grams of propionic acid containing 1.0 gram of COBI'26H2O (ii) Operation according to the invention The above experiment was repeated in identical manner except that 6.0 grams of sodium hydroxide was 6 added. The following results were obtained.
Volume percent in ofl-gas of.
at the boiling point of the liquid (137 C.) underatmospheric pressure for 7 hours. Analysis of the'exit gas stream showed 28.6 volume percent of carbon dioxide and 12 grams of water, which is clear evidence of considerable degradative oxidation of the propionic acid.
Operating according to the invention, 200 grams of propionic acid containing 1.0 gram of CoBr 6H O and 5.0 grams of sodium bromide was treated in exactly EXAMPLE 4 The experiments described in Example 3 were repeated using acetic acid (600 grams) in place of propionic acid.
0 The results, given below, show that in this case also oxidative degradation is suppressed by addition of the sodium similar manner as in the blank experiment. Analysis of 011- Time: hours 0.25 1.25 2.25 3.25 4.25 5.25 6.25 7.25 Experiment 00, 1.4 0.0 0.7 1.0 0.8 0 5 0.7 0.8 }With0ut sodium V 1 in ft f 00 1.2 1.0 0 0 0 0 0 0 wliyhdrolxlidg. mepemem -co, 0s 0s '02 02 02 05 0s 02{ sodium by Co 1.0 0 0 0 0 0 0 0 mm EXAMPLE 5 ''the' exit gas stream showed the absence of carbon dioxide and of water.
This is clear evidence of the inhibition of degradative oxidation of the propionic acid.
The experiments described in Example 3 were repeated except that barium hydroxide, .Ba(OH) .8H O (4,7,.3
grams) was added in place of sodium hydroxide. The results given below indicate that barium is eifective also in suppressing oxidative degradation. The blank experiment was carried out immediately before the run using barium, in order to be certain that conditions were such that degradation would still occur, i.e., that no sodium remained in the reactor.
(NaOAc.3H O). In this case also oxygen uptake was almost complete and the reaction over in 5 hours. The product weighed 252.7 grams, and 1.3 grams of material was collected in the cold catch-pots.
In contrast, however, the carbon dioxide content of the exit gas in this run was extremely small, and analysis of the reaction product as in (i) showed the following yields Time: hours 0.25 1.25 2.25 3.25 4.25 5.25 6.25 7.25 Experiment wit out ar um. Vmumepelcentmmgawt CO: 0 1.0 0.5 0.5 0.5 1.0 1.0 }With barium hy- 00 0 0 0 0 0 0 0 0 droxlde added.
EXAMPLE 6 based on propionaldehyde remaining in the reactor:'
This illustrates the use of sodium ion to suppress degradation in the autoxidation of propionaldehyde to propionic acid.
(i) Blank The charge consisting of 200 grams of propionaldehyde/water azeotrope (98% propionaldehyde) and 0.1 gram of manganese acetate (Mn(AOc) .4I-I O), was held in a glass reactor and 12 litres/hour of oxygen was introduced at atmospheric pressure through the hollow shaft of a cruciform stirrer revolving in the reaction mixture at 1000 r.p.m. The ofi-gas line from the reactor contained two water condensers and two cold catch-pots. The temperature in the reactor was held at 25 to 30 C. by means of an external cooling bath containing circulating water. The off-gas from the reactor was mixed with air fed at 12 litres/ hour and frequent Orsat analyses of the mixtures were carried out for oxygen and carbon oxides. Oxygen uptake was rapid and almost complete, and ceased after 5 hours. Thereafter the oxidation was stopped.
During most of the oxidation the off-gas contained 8 to 10% by volume of carbon dioxide. Separation and estimation of acids in the reaction product (228.0 grams), by means of liquid phase partition chromatography, estimation of aldehyde polargraphically, and estimation of propyl propionate by ester value, indicated the following yields based on propionaldehyde remaining in the reactor, due allowance being made for material entrained and collected in the catch-pots (7.6 grams).
Percentage conversion of propionaldehyde 7 a by weight to: Y
Formic acid 0 Acetic acid 0 Propionic acid 91.7 Propyl propionate 3.6 Unchanged 0.9
Totally to carbon oxides and unaccounted for 3.8
Clearly, the addition of sodium acetate actively suppresses oxidative degradation to lower acids and oxides of carbon and causes a substantial increase in the yield of propionic acid.
EXAMPLE 7 It has been shown above that the presence of basic ion greatly decreases the oxidative degradation of propionic acid. The data given below show that the presence of alkali metal ion does not adversely aifect the oxidation of an alkyl aromatic compound in propionic acid as solvent.
The oxidation of para-xylene (40 grams) dissolved in propionic acid (200 grams) was performed in the presence of the catalysts specified in the table below at the boiling point (about 137 C.) using an oxygen rate of 12 litres per hour. The concentrations of manganese and cobalt in runs 1 and 2 are the same as in runs 3 and 4.
Catalyst Purity of Molar Weight of terephconversion Run No. Time, terephthalic acid to tereph- Manganese Cobalt Additive, hours thalic acid, by acid thalic compound, compound, grams grams value, acid,
grams grams percent percent Mn(Ac)z 00(Ac); NaBr 0.2 0.1 5.0 7 47.0 96.6 72.6 0.2 0.1 5.0 20 57.9 97.4 90.1 MllBlg4HgO COB12.6H20
Percentage conversion of propionaldehyde Thus run 2, in which 0.016 gram atom of sodium was by weight to: present per gram mole of total organic compound, gave Formic acid 0.7 quite as good molar conversion of para-xylene to tereph- Acetic acid 6.4 thalic acid in 20 hours and therefore quite as high a Propionic acid 81.3 reaction velocity as run 4 in which no sodium was present, Propyl propionate 5.1 and this under conditions Which cause very little oxida- Unchanged 1.0 tive degradation of propionic acid. Totally to carbon oxides and unaccounted I claim:
for 5.5 1. In processes for the production of carboxylic acids by oxidation in the liquid phase of at least one member 100.0 selected from the group consisting of aliphatic aldehydes,
(ii) Operation according to the invention A run was carried out exactly as above, except that the charge contained 5.0 grams of sodium acetate alkyl aromatic hydrocarbons, alkyl aromatic heterocyclic compounds, having alkyl groups as the sole substituents, and closely related oxygenated derivatives of these classes of compounds; with oxygen gas in the presence of a bromine compound and as catalyst a metal selected from the group consisting of cobalt and manganese, and in the presence of a saturated aliphatic monocarboxylic acid, the improvement which consists in inhibiting the oxidative degradation of said aliphatic monocarboxylic acid by conducting said process in the further presence of a cation selected from the group consisting of alkali and alkaline earth metal compounds in an amount corresponding to a concentration within the range of from 0.25 to 0.00025 gram atom per gram mole of total organic compounds.
2. A process as claimed in claim 1, in which the starting material is propionaldehyde and propionic acid is produced.
3. A process as claimed in claim 1, in which said concentration of said cation corresponds to from 0.05 to 0.0025 gram atom.
4. A process as claimed in claim 1, wherein said starting material is xylenes.
5. A process as claimed in claim 1, wherein said starting material is di-isopropyl benzene.
6. A process as claimed in claim 1, wherein said starting material is toluene.
.7. A process as claimed in claim 1, wherein said starting material is cumene.
8. A process as claimed in claim 1, wherein said starting material is para-toluic acid.
References Cited in the file of this patent UNITED STATES PATENTS 2,223,494 Loder Dec. 3, 1940 2,245,528 Loder June 10, 1941 2,287,537 Schulz June 23, 1942 2,444,924 Farkas et al July 13, 1948 2,833,778 Safler et al May 6, 1958 2,833,816 Safier et al May 6, 1958
Claims (1)
1. IN PROCESSES FOR THE PRODUCTION OF CARBOXYLIC ACIDS BY OXIDATION IN THE LIQUID PHASE OF AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC ALDEHYDES, ALKYL AROMATIC HYDROCARBONS, ALKYL AROMATIC HETEROCYCLIC COMPOUNDS, HAVING ALKYL GROUPS AS THE SOLE SUBSTITUENTS, AND CLOSELY RELATED OXYGENATED DERIVATIVES OF THESE CLASSES OF COMPOUNDS, WITH OXYGEN GAS IN THE PRESENCE OF A BROMINE COMPOUND AND AS CATALYST A METAL SELECTED FROM THE GROUP CONSISTING OF COBALT AND MANGANESE, AND IN THE PRESENCE OF A SATURATED ALIPHATIC MONOCARBOXYLIC ACID, THE IMPROVEMENT WHICH CONSISTS IN INHIBITING THE OXIDATIVE DEGRADATION OF SAID ALIPHATIC MONOCARBOXYLIC ACID BY CONDUCTING SAID PROCESS IN THE FURTHER PRESENCE OF A CATION SELECTED FROM THE GROUP CONSISTING OF ALKALI AND ALKALINE EARTH METAL COMPOUNDS IN AN AMOUNT CORRESPONDING TO A CONCENTRATION WITHIN THE RANGE OF FROM 0.25 TO 0.00025 GRAM ATOM PER GRAM MOLE OF TOTAL ORGANIC COMPOUNDS.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3053854A (en) * | 1959-06-04 | 1962-09-11 | Scient Design Co | Purification of phthalic anhydride |
| US3091636A (en) * | 1963-05-28 | Process for the production of | ||
| US3151153A (en) * | 1958-09-30 | 1964-09-29 | Sinclair Research Inc | Preparation of sulfobenzene carboxylic acid |
| US3260682A (en) * | 1961-01-25 | 1966-07-12 | Distillers Co Yeast Ltd | Catalyst compositions consisting of cobalt molybdate and various molybdate hardeners |
| US3299125A (en) * | 1963-05-01 | 1967-01-17 | Teijin Ltd | Process for the preparation of aromatic carboxylic acids |
| US3351657A (en) * | 1962-02-23 | 1967-11-07 | Ici Ltd | Production of oxygen-containing organic compounds by the co-oxidation of cycloparaffins and aldehydes |
| US3453324A (en) * | 1966-01-03 | 1969-07-01 | Monsanto Co | Preparation of aromatic acids from hydroxymethylaromatics |
| US3679740A (en) * | 1969-12-17 | 1972-07-25 | Universal Oil Prod Co | Preparation of aromatic acids |
| US4113782A (en) * | 1975-02-18 | 1978-09-12 | Agency Of Industrial Science And Technology | Process for the preparation of formylated phenoxy compounds |
| JPS61246143A (en) * | 1985-04-24 | 1986-11-01 | Teijin Yuka Kk | Production of 2,6-naphthalenedicarboxylic acid |
| US5215671A (en) * | 1990-06-11 | 1993-06-01 | Mitsui Toatsu Chemicals, Incorporated | Purification method of 2-chloropropionic acid |
| US5686638A (en) * | 1994-09-06 | 1997-11-11 | Dsm Chemie Linz Gmbh | Process for the preparation of mono- or dicarboxylic acids from aldehydes, from their full acetals or hemiacetals or from mixtures thereof |
| US20080103332A1 (en) * | 2006-11-01 | 2008-05-01 | David Yen | Method of manufacturing pta oxidized catalyst with lower corrosion |
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| US2223494A (en) * | 1939-06-06 | 1940-12-03 | Du Pont | Production of cyclic alcohols and ketones |
| US2444924A (en) * | 1944-10-01 | 1948-07-13 | Farkas Ladislaus Guillaume | Process of oxidizing primary or secondary alcoholic hydroxyl groups or aldehyde groups |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3091636A (en) * | 1963-05-28 | Process for the production of | ||
| US3151153A (en) * | 1958-09-30 | 1964-09-29 | Sinclair Research Inc | Preparation of sulfobenzene carboxylic acid |
| US3053854A (en) * | 1959-06-04 | 1962-09-11 | Scient Design Co | Purification of phthalic anhydride |
| US3260682A (en) * | 1961-01-25 | 1966-07-12 | Distillers Co Yeast Ltd | Catalyst compositions consisting of cobalt molybdate and various molybdate hardeners |
| US3351657A (en) * | 1962-02-23 | 1967-11-07 | Ici Ltd | Production of oxygen-containing organic compounds by the co-oxidation of cycloparaffins and aldehydes |
| US3299125A (en) * | 1963-05-01 | 1967-01-17 | Teijin Ltd | Process for the preparation of aromatic carboxylic acids |
| US3453324A (en) * | 1966-01-03 | 1969-07-01 | Monsanto Co | Preparation of aromatic acids from hydroxymethylaromatics |
| US3679740A (en) * | 1969-12-17 | 1972-07-25 | Universal Oil Prod Co | Preparation of aromatic acids |
| US4113782A (en) * | 1975-02-18 | 1978-09-12 | Agency Of Industrial Science And Technology | Process for the preparation of formylated phenoxy compounds |
| JPS61246143A (en) * | 1985-04-24 | 1986-11-01 | Teijin Yuka Kk | Production of 2,6-naphthalenedicarboxylic acid |
| US5215671A (en) * | 1990-06-11 | 1993-06-01 | Mitsui Toatsu Chemicals, Incorporated | Purification method of 2-chloropropionic acid |
| US5686638A (en) * | 1994-09-06 | 1997-11-11 | Dsm Chemie Linz Gmbh | Process for the preparation of mono- or dicarboxylic acids from aldehydes, from their full acetals or hemiacetals or from mixtures thereof |
| US20080103332A1 (en) * | 2006-11-01 | 2008-05-01 | David Yen | Method of manufacturing pta oxidized catalyst with lower corrosion |
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